The present invention relates to a process for producing a solid catalyst component for xcex1-olefin polymerization, a process for producing a catalyst for xcex1-olefin polymerization, and a process for producing an xcex1-olefin polymer.
As a catalyst for a high stereospecificity polymerization of an xcex1-olefin, the following catalysts are known.
(1) A catalyst obtained by combining a support type solid catalyst component prepared by supporting a tetravalent titanium halide on a magnesium halide with an organoaluminum compound as a co-catalyst and an organosilicon compound as a third component (refer to JP-A 57-63310, JP-A 58-83006 and JP-A 61-78803).
(2) A catalyst obtained by combining a trivalent titanium compound-containing solid catalyst component with an organoaluminum compound as a co-catalyst and an electron donor compound as a third component, wherein the trivalent titanium compound-containing solid catalyst component is prepared by reducing a titanium compound with an organomagnesium compound in the presence of both an organosilicon compound and an ester compound to obtain a solid product, and treating the solid product with an ester compound, followed by successive treatment with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound (refer to JP-A 7-216017).
(3) A catalyst obtained by combining a trivalent titanium compound-containing solid catalyst component with an organoaluminum compound as a co-catalyst and an electron donor compound as a third component, wherein the trivalent titanium compound-containing solid catalyst component is prepared by reducing a titanium compound with an organomagnesium compound in the presence of both an organosilicon compound and an ester compound to obtain a solid product, and treating the solid product with a mixture of an ether compound and titanium tetrachloride, followed by successive treatment with an organic acid halide compound, and further followed by successive treatment with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound (refer to JP-A 10-212319).
However, an xcex1-olefin polymer obtained by polymerization using any of catalysts mentioned above does not have stereospecificity of a satisfactory level, from a viewpoint of the facts that (1) a molded article having a higher rigidity is desired particularly in the field of injection molding, and (2) rigidity of an injection-molded article is increased with increase in stereospecificity of a polymer to be used.
An object of the present invention is to provide a process for producing a catalyst for xcex1-olefin polymerization, which catalyst has a high polymerization activity and a stereospecificity polymerization ability of a high level so that removal of an amorphous polymer is not needed.
Another object of the present invention is to provide a process for producing a solid catalyst component used for the production of such a catalyst.
A further object of the present invention is to provide a process for producing an xcex1-olefin polymer by using such a catalyst.
The present invention provides a process for producing a solid catalyst component (1) for xcex1-olefin polymerization, which comprises the steps of:
(1) reducing a titanium compound represented by the following formula [I] with an organomagnesium compound in the presence of an organosilicon compound having an Sixe2x80x94O bond, thereby obtaining a solid product, and
(2) contacting the solid product with at least one member selected from the group consisting of an electron donor compound (E1) and an organic acid halide, and a compound having a Ti-halogen bond, thereby obtaining the solid catalyst component (1) for xcex1-olefin polymerization, 
wherein xe2x80x9caxe2x80x9d is a number of 2 to 20, R2 is a hydrocarbon group having 1 to 20 carbon atoms, and X2 is a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms, and all of X2 may be the same or different from one another.
The present invention also provides a process for producing a solid catalyst component (2) for xcex1-olefin polymerization, which comprises the steps of:
(1) reducing a titanium compound represented by the above formula [I] with an organomagnesium compound in the presence of an organosilicon compound having an Sixe2x80x94O bond and an ester compound, thereby obtaining a solid product, and
(2) contacting the solid product with at least one member selected from the group consisting of an electron donor compound (E1) and an organic acid halide, and a compound having a Ti-halogen bond, thereby obtaining the solid catalyst component (2) for xcex1-olefin polymerization.
The present invention further provides a process for producing a catalyst (1) for xcex1-olefin polymerization, which comprises the steps of:
(1) reducing a titanium compound represented by the above formula [I] with an organomagnesium compound in the presence of an organosilicon compound having an Sixe2x80x94O bond, thereby obtaining a solid product,
(2) contacting the solid product with at least one member selected from the group consisting of an electron donor compound (E1) and an organic acid halide, and a compound having a Ti-halogen bond, thereby obtaining a solid catalyst component (1) for xcex1-olefin polymerization, and
(3) contacting the solid catalyst component (1), an organoaluminum compound and an electron donor compound (E2) with one another, thereby obtaining the catalyst (1) for xcex1-olefin polymerization.
The present invention still further provides a process for producing a catalyst (2) for xcex1-olefin polymerization, which comprises the steps of:
(1) reducing a titanium compound represented by the above formula [I] with an organomagnesium compound in the presence of an organosilicon compound having an Sixe2x80x94O bond and an ester compound, thereby obtaining a solid product,
(2) contacting the solid product with at least one member selected from the group consisting of an electron donor compound (E1) and an organic acid halide, and a compound having a Ti-halogen bond, thereby obtaining a solid catalyst component (2) for xcex1-olefin polymerization, and
(3) contacting the solid catalyst component (2), an organoaluminum compound and an electron donor compound (E2) with one another, thereby obtaining the catalyst (2) for xcex1-olefin polymerization.
The present invention additionally provides a process for producing an xcex1-olefin polymer, which comprises the steps of:
(1) reducing a titanium compound represented by the above formula [I] with an organomagnesium compound in the presence of an organosilicon compound having an Sixe2x80x94O bond compound, thereby obtaining a solid product,
(2) contacting the solid product with at least one member selected from the group consisting of an electron donor compound (E1) and an organic acid halide, and a compound having a Ti-halogen bond, thereby obtaining a solid catalyst component (1) for xcex1-olefin polymerization,
(3) contacting the solid catalyst component (1), an organoaluminum compound and an electron donor compound (E2) with one another, thereby obtaining a catalyst (1) for xcex1-olefin polymerization, and
(4) subjecting an xcex1-olefin to homopolymerization or copolymerization in the presence of the catalyst (1).
The present invention still additionally provides a process for producing an xcex1-olefin polymer, which comprises the steps of:
(1) reducing a titanium compound represented by the above formula [I] with an organomagnesium compound in the presence of an organosilicon compound having an Sixe2x80x94O bond and an ester compound, thereby obtaining a solid product,
(2) contacting the solid product with at least one member selected from the group consisting of an electron donor compound (E1) and an organic acid halide, and a compound having a Ti-halogen bond, thereby obtaining a solid catalyst component (2) for xcex1-olefin polymerization,
(3) contacting the solid catalyst component (2), an organoaluminum compound and an electron donor compound (E2) with one another, thereby obtaining a catalyst (2) for xcex1-olefin polymerization, and
(4) subjecting an xcex1-olefin to homopolymerization or copolymerization in the presence of the catalyst (2).
In the present invention, the solid catalyst components (1) and (2) for xcex1-olefin polymerization are hereinafter together referred to as xe2x80x9csolid catalyst componentxe2x80x9d for brevity, and the catalysts (1) and (2) for xcex1-olefin polymerization are also hereinafter together referred to as xe2x80x9ccatalystxe2x80x9d for brevity.
Electron Donor Compound (E1)
Examples of the electron donor compound (E1) used for the production of the solid catalyst component in accordance with the present invention are oxygen-containing compounds such as ethers (containing diethers), ketones, aldehydes, carboxylic acids, organic acid esters, inorganic acid esters, organic acid amides, inorganic acid amides and acid anhydrides; and nitrogen-containing compounds such as ammonia, amines, nitriles and isocyanates. Of these, organic acid esters and ethers are preferred, carboxylic acid esters and diethers are more preferred, and carboxylic acid esters are most preferred.
As the carboxylic acid esters, for example, mono-carboxylic acid esters and poly-carboxylic acid esters are enumerated. More specifically, saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters and aromatic carboxylic acid esters are enumerated.
Specific examples of the carboxylic acid esters are methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-i-propyl phthalate, di-n-butyl phthalate, di-i-butyl phthalate, di-n-octyl phthalate and diphenyl phthalate.
Among these carboxylic acid esters, unsaturated aliphatic carboxylic acid esters such as methacrylic acid esters and maleic acid esters, and aromatic carboxylic acid esters such as benzoic acid esters and phthalic acid esters are preferred, and aromatic polycarboxylic acid esters are particularly preferred. Of these, dialkyl phthalates are most preferred.
Preferred diethers are those represented by the following formula, 
wherein R5 to R8 are independently of one another a straight- or branched-chain or alicyclic alkyl group having 1 to 20 carbon atoms; an aryl group; or an aralkyl group, provided that R6 and R7 may be independently of each other a hydrogen atom.
Specific examples of the diethers are 2,2-di-i-butyl-1,3-dimethoxypropane, 2-i-propyl-2-i-pentyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-i-propyl-2-3,7-dimethyloctyl-1,3-dimethoxypropane, 2,2-di-i-propyl-1,3-dimethoxypropane, 2-i-propyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-i-propyl-2-i-butyl-1,3-dimethoxypropane, 2,2-di-i-propyl-1,3-dimethoxypropane, 2,2-di-propyl-1,3-dimethoxypropane, 2-i-propyl-2-cyclohexyl-1,3-dimethoxypropane, 2-i-propyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-di-cyclopentyl-1,3-dimethoxypropane and 2-heptyl-2-pentyl-1,3-dimethoxypropane.
Among diethers represented by the above formula, preferred diethers are those having the alkyl group as R5 to R8 which are independent of each other, and more preferred are those having the branched-chain or alicyclic alkyl group as R6 and R7 which are independent of each other, and the straight-chain alkyl group as R5 and R8 which are independent of each other.
Organic Acid Halide
A preferred organic acid halide used in the present invention is mono- or poly-carboxylic acid halides. As the organic acid halides, for example, aliphatic carboxylic acid halides, alicyclic carboxylic acid halides and aromatic carboxylic acid halides are enumerated. Specific examples of the organic acid halides are acetyl chloride, propionic chloride, butyric chloride, valeric chloride, acrylic chloride, methacrylic chloride, benzoic chloride, toluic chloride, anisic chloride, succinic chloride, malonic chloride, maleic chloride, itaconic chloride and phthalic chloride. Of these, aromatic carboxylic acid chlorides such as benzoic chloride, toluic chloride and phthalic chloride are preferred. Aromatic dicarboxylic acid dichlorides are more preferred, and phthalic chloride is particularly preferred.
Compound Having a Ti-Halogen Bond
A preferred compound having a Ti-halogen bond used in the present invention is a titanium compound represented by the following formula,
Ti(OR9)bX44xe2x88x92b 
wherein R9 is a hydrocarbon group having 1 to 20 carbon atoms, X4 is a halogen atom, and b is a number satisfying 0xe2x89xa6b less than 4.
Examples of R9 are alkyl groups such as methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, amyl, i-amyl, tert-amyl, hexyl, heptyl, octyl, decyl and dodecyl groups; aryl groups such as phenyl, cresyl, xylyl and naphthyl groups; allyl group; and aralkyl groups such as a benzyl group. Among these R9, alkyl groups having 2 to 18 carbon atoms and aryl groups having 6 to 18 carbon atoms are preferred, and straight-chain alkyl groups having 2 to 18 carbon atoms are particularly preferred. As the compound represented by the above formula, it is allowed to use those having two or more OR9 groups different from one another.
As X4 in the above formula, a chlorine atom, a bromine atom and an iodine atom are exemplified. Of these, a chlorine atom is particularly preferred.
A preferred b in the above formula is a number satisfying 0xe2x89xa6bxe2x89xa62, and a particularly preferred b is 0.
Specific examples of the titanium compound represented by the above formula are titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide; hydrocarbyloxytitanium trihalides such as methoxytitanium trichloride, ethoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, and ethoxytitanium tribromide; and dihydrocarbyloxytitanium dihalides such as dimethoxytitanium dichloride, diethoxytitanium dichloride, dibutoxytitanium dichloride, diphenoxytitanium dichloride, and diethoxytitanium dibromide. Among these titanium compounds, the most preferred is titanium tetrachloride.
Organosilicon Compound Having an Sixe2x80x94O Bond
Preferable examples of the organosilicon compound having an Sixe2x80x94O bond are, for example, those represented by any one of the following formulas,
Si(OR10)tR114xe2x88x92t, 
R12(R132SiO)uSiR143 and 
(R152SiO)v 
wherein R10 is a hydrocarbon group having 1 to 20 carbon atoms, R11, R12, R13, R14 and R15 are independently of one another a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, t is a number satisfying 0 less than txe2x89xa64, u is an integer of from 1 to 1000, and v is an integer of from 2 to 1000.
Specific examples of the organosilicon compound are tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetra-i-propoxysilane, di-i-propoxy-di-i-propylsilane, tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane, hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, octaethyltrisiloxane, dimethyl polysiloxane, diphenyl polysiloxane, methylhydro polysiloxane and phenylhydro polysiloxane.
Among these, more preferable are alkoxysilane compounds represented by the formula Si(OR10)tR114xe2x88x92t, wherein t is preferably a number satisfying 1xe2x89xa6bxe2x89xa64. Of these, tetraalkoxysilane compounds of t=4 are particularly preferred, and the most preferred is tetraethoxysilane.
Titanium Compound
Examples of R2 in the above formula [I] representing the titanium compound used in the present invention are alkyl groups such as methyl, ethyl, propyl, i-propyl, butyl, i-butyl, amyl, i-amyl, hexyl, heptyl, octyl, decyl and dodecyl groups; aryl groups such as phenyl, cresyl, xylyl and naphthyl groups: cycloalkyl groups such as cyclohexyl and cyclopentyl groups; allyl groups such as a propenyl group; and aralkyl groups such as a benzyl group. Among these, alkyl groups having 2 to 18 carbon atoms and aryl groups having 6 to 18 carbon atoms are preferred, and straight-chain alkyl groups having 2 to 18 carbon atoms are particularly preferred.
As the halogen atom represented by X2 in the above formula [I], a chlorine atom, a bromine atom and an iodine atom are exemplified. Of these, a chlorine atom is particularly preferred. As the oxyhydrocarbon groups having 1 to 20 carbon atoms represented by X2 in the above formula [I], an alkoxy group having a straight-chain alkyl group of 2 to 18 carbon atoms is particularly preferred. A preferred xe2x80x9caxe2x80x9d in the above formula [I] is a number satisfying 2xe2x89xa6axe2x89xa65, and a more preferred xe2x80x9caxe2x80x9d is 2 or 4.
As specific examples of the titanium compound, tetra-i-propyl polytitanate (a mixture of compounds of xe2x80x9caxe2x80x9d=2xcx9c10), tetra-n-butyl polytitanate (a mixture of compounds of xe2x80x9caxe2x80x9d=2xcx9c10), tetra-n-hexyl polytitanate (a mixture of compounds of xe2x80x9caxe2x80x9d=2xcx9c10) and tetra-n-octyl polytitanate (a mixture of compounds of xe2x80x9caxe2x80x9d=2xcx9c10) are exemplified. As such a compound, a condensate of a tetraalkoxytitanium obtained by reacting a tetralkoxytitanium with a small amount of water is further exemplified. Of these, tetra-n-butyl polytitanate is more preferred, and tetra-n-butyltitanium dimer or tetra-n-butyltitanium tetramer is particularly preferred.
It is permitted to use the titanium compound mentioned above in combination with a titanium compound represented by the following formula,
Ti(OR2)qX34xe2x88x92q 
wherein R2 is a hydrocarbon group having 1 to 20 carbon atoms, X3 is a halogen atom, and q is a number satisfying 0 less than qxe2x89xa64.
Organomagnesium Compound
The xe2x80x9corganomagnesium compoundxe2x80x9d used in the present invention means any types of organomagnesium compounds having a magnesium-carbon bond. As the organomagnesium compound, a Grignard compound represented by the following first formula, and a dihydrocarbyl magnesium compound represented by the following second formula are particularly suitable.
R16MgX5 
In this formula, Mg is a magnesium atom, R16 is a hydrocarbon group having 1 to 20 carbon atoms and X5 is a halogen atom.
R17R18Mg 
In this formula, Mg is a magnesium atom, R17 and R18 are independently of each other a hydrocarbon group having 1 to 20 carbon atoms.
In the above second formula, R17 and R18 may be the same or different from each other. Specific examples of R16 to R18 are alkyl, aryl, aralkyl and alkenyl groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, tert-butyl, i-amyl, hexyl, octyl, 2-ethylhexyl, phenyl and benzyl groups. It is particularly recommendable to use the Grignard compound represented by the above first formula in the form of an ether solution thereof from a viewpoint of polymerization activity of the catalyst obtained.
It is permitted to use the organomagnesium compound in combination with an organometallic compound to form a hydrocarbon soluble complex. Examples of the organometallic compounds are compounds of Li, Be, B, Al and Zn.
Ester Compound
In the present invention, it is recommendable to use an ester compound from a viewpoint of improving a polymerization activity and a stereospecificity polymerization ability of the catalyst obtained. The xe2x80x9cester compoundxe2x80x9d means a mono- or poly-carboxylic acid ester. As the ester compound, for example, saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters and aromatic carboxylic acid esters are enumerated. Specific examples of the ester compounds are methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-i-propyl phthalate, di-n-butyl phthalate, di-i-butyl phthalate, di-n-octyl phthalate and diphenyl phthalate.
Among these ester compounds, unsaturated aliphatic carboxylic acid esters such as methacrylic acid esters and maleic acid esters and aromatic carboxylic acid esters such as phthalic acid esters are preferred. Dialkyl phthalates are particularly preferred.
Solid Product
The organosilicon compound, the titanium compound and the ester compound, which are used for the production of the solid product, are preferably dissolved in or diluted with a suitable solvent, and then used therefor. Examples of the solvent are aliphatic hydrocarbons such as hexane, heptane, octane and decane; aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin; and ether compounds such as diethyl ether, dibutyl ether, di-i-amyl ether and tetrahydrofuran.
A temperature of the reduction reaction is usually from xe2x88x9250 to 70xc2x0 C., preferably from xe2x88x9230 to 50xc2x0 C., and particularly preferably from xe2x88x9225 to 35xc2x0 C. A time required for the reduction reaction is not particularly limited, and it is usually from about 30 minutes to about 6 hours. After the reaction is carried out at the above-mentioned temperature, it is permitted to further carry out a post-reaction at a temperature of from 20 to 120xc2x0 C.
The reduction reaction may be carried out in the presence of a porous carrier such as inorganic oxides and organic polymers, whereby the solid product produced can be supported on the porous carrier. The porous carrier may be conventional ones. Examples of the porous carrier are porous inorganic oxides such as SiO2, Al2O3, MgO, TiO2 and ZrO2; and organic porous polymers such as polystyrene, styrene-divinylbenzene copolymer, styrene-ethylene glycol-methyl dimethacrylate copolymer, polymethylacrylate, polyethylacrylate, methyl acrylate-divinylbenzene copolymer, polymethylmethacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, polyethylene and polypropylene. Of these, organic porous polymers are preferred, and styrene-divinylbenzene copolymer and acrylonitrile-divinylbenzene copolymer are particularly preferred.
With respect to the porous carriers, (i) a volume of micro pores having a radius of from 200 to 2000 xc3x85 is preferably 0.3 cc/g or more, and more preferably 0.4 cc/g or more, and (ii) a proportion of the volume of micro pores having a radius of from 200 to 2000 xc3x85 is preferably 35% or more, and more preferably 40% or more, provided that a volume of micro pores having a radius of from 35 to 75000 xc3x85 is assigned to be 100%. It is not recommendable to use a porous carrier having too small micro pore volume, because the catalyst component is not supported on the carrier effectively. Meanwhile, even if a porous carrier has a micro pore volume of 0.3 cc/g or more, the catalyst component is not supported on the carrier effectively when the porous carrier does not satisfy its micro pore radius of from 200 to 2000 xc3x85.
The organosilicon compound is used in an amount of usually from 1 to 500, preferably from 1 to 300, and more preferably from 3 to 100 in terms of an atomic ratio Si/Ti, i.e. a ratio of a silicon atom in the organosilicon compound to a titanium atom in the titanium compound.
The organomagnesium compound is used in an amount of usually from 0.1 to 10, preferably from 0.2 to 5.0, and more preferably from 0.5 to 2.0 in terms of an atomic ratio (Ti+Si)/Mg, i.e. a ratio of the sum of a titanium atom in the titanium compound and a silicon atom in the organosilicon compound to a magnesium atom in the organomagnesium compound.
Alternatively, it is permitted that respective amounts of the titanium compound, the organosilicon compound and the organomagnesium compound are determined so as to make a molar ratio of Mg/Ti in the solid catalyst component from 1 to 51, preferably from 2 to 31, and more preferably from 4 to 26.
The ester compound is used in an amount of usually from 0.5 to 100, preferably from 1 to 60, and more preferably from 2 to 30 in terms of a molar ratio, ester compound/Ti, i.e. a ratio of the ester compound to a titanium atom in the titanium compound.
The solid product obtained by the reduction reaction is separated usually by solid-liquid separation, and washed several times with an inert hydrocarbon solvent such as hexane and heptane. The thus obtained solid product contains a trivalent titanium atom, a magnesium atom and a hydrocarbyloxy group, and in general has an amorphous structure or an extremely low crystallinity. A solid product having the amorphous structure is particularly preferred from a viewpoint of catalyst performance.
Solid Catalyst Component
In a process for obtaining the solid catalyst component by contacting the above-mentioned solid product with at least one member selected from the group consisting of the electron donor compound (E1) and the organic acid halide, and the compound having a Ti-halogen bond, all of respective contacts are usually carried out under atmosphere of an inert gas such as nitrogen and argon.
Said contact can be carried out, for example, by the following methods (1) to (4), wherein each contact may be repeated several times.
(1) The solid product is contacted with at least one member selected from the group consisting of the electron donor compound (E1) and the organic acid halide, followed by successive contact with the compound having a Ti-halogen bond.
(2) The solid product is contacted with a mixture of at least one member selected from the group consisting of the electron donor compound (E1) and the organic acid halide, and the compound having a Ti-halogen bond, followed by successive contact with the compound having a Ti-halogen bond.
(3) The solid product is contacted with the compound having a Ti-halogen bond, followed by successive contact with at least one member selected from the group consisting of the electron donor compound (E1) and the organic acid halide.
(4) The solid product is contacted with the compound having a Ti-halogen bond, followed by successive contact with at least one member selected from the group consisting of the electron donor compound (E1) and the organic acid halide, and further followed by successive contact with the compound having a Ti-halogen bond.
Preferred solid catalyst components are those obtained by the below mentioned processes (1) and (2). (1) A solid catalyst component obtained by a process wherein the solid product is contacted with the electron donor compound (E1), followed by successive contact with the compound having a Ti-halogen bond.
(2) A solid catalyst component obtained by a process here in the solid product is contacted with the compound having a Ti-halogen bond and the organic acid halide, followed by successive contact with the electron donor compound (E1) and the compound having a Ti-halogen bond.
More preferred solid catalyst components are those obtained by the below mentioned processes (1) to (6).
(1) A solid catalyst component obtained by a process wherein the solid product is contacted with the electron donor compound (E1), followed by successive contact with the compound having a Ti-halogen bond.
(2) A solid catalyst component obtained by a process wherein the solid product is contacted with the electron donor compound (E1), followed two times by successive contact with the compound having a Ti-halogen bond.
(3) A solid catalyst component obtained by a process wherein the solid product is contacted with the electron donor compound (E1), followed two times by successive contact with a mixture of the electron donor compound (E1) and the compound having a Ti-halogen bond.
(4) A solid catalyst component obtained by a process wherein the solid product is contacted with the compound having a Ti-halogen bond and the organic acid halide, followed by successive contact with the compound having a Ti-halogen bond.
(5) A solid catalyst component obtained by a process wherein the solid product is contacted with the compound having a Ti-halogen bond and the organic acid halide, followed three times by successive contact with the compound having a Ti-halogen bond.
(6) A solid catalyst component obtained by a process wherein the solid product is contacted with the electron donor compound (E1), the compound having a Ti-halogen bond and the organic acid halide, followed three times by successive contact with a mixture of the electron donor compound (E1) and the compound having a Ti-halogen bond.
Particularly preferred solid catalyst components are those obtained by the below mentioned processes (1) to (3).
(1) A solid catalyst component obtained by a process wherein the solid product is contacted with the electron donor compound (E1), followed two times by successive contact with a mixture of the electron donor compound (E1) and the compound having a Ti-halogen bond.
(2) A solid catalyst component obtained by a process wherein the solid product is contacted with a mixture of the electron donor compound (E1), the compound having a Ti-halogen bond and the organic acid halide, followed three times by successive contact with a mixture of the electron donor compound (E1) and the compound having a Ti-halogen bond.
(3) A solid catalyst component obtained by a process wherein the solid product is contacted with a mixture of the electron donor compound (E1) and the compound having a Ti-halogen bond, followed by successive contact with the organic acid halide, and further followed three times by successive contact with a mixture of the electron donor compound (E1) and the compound having a Ti-halogen bond.
The above-mentioned contact can be carried out by a conventional method such as a slurry method and a mechanical pulverization method using a ball mill. However, the latter is not recommendable from an industrial point of view, because a lot of fine powders may be produced to make a particle size distribution of the solid catalyst component obtained broad. Therefore, it is recommendable to carry out the contact in the presence of a diluent mentioned below.
Respective solids obtained by the above-mentioned contacts can be used as they are for the successive contact. However, it is recommendable to wash the solid with a diluent mentioned below, thereby removing unnecessaries contained in the solid.
The diluent is preferably a compound inert to the materials to be treated. Examples thereof are aliphatic hydrocarbons such as pentane, hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic hydrocarbons such as cyclohexane and cyclopentane; and halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene.
When the diluent is used during the above-mentioned contact, an amount of the diluent per contact is usually from 0.1 ml to 1000 ml, and preferably from 1 ml to 100 ml per g of the solid product. When the diluent is used for the washing as mentioned above, an amount thereof per washing is similar to that in the contact. The washing is carried out usually from 1 to 5 times per contact.
The contact and washing can be carried out usually at a temperature of from xe2x88x9250 to 150xc2x0 C., preferably from 0 to 140xc2x0 C., and more preferably from 60 to 135xc2x0 C. A time for the contact is not particularly limited. It is preferably from 0.5 to 8 hours, and more preferably from 1 to 6 hours. Also, a time for the washing is not particularly limited. It is preferably from 1 to 120 minutes, and more preferably from 2 to 60 minutes.
The electron donor compound (E1) is used in an amount of usually from 0.1 to 50 mol, preferably from 0.3 to 30 mol, and more preferably from 0.5 to 20 mol per mol of the titanium atom in the solid product. When the amount is too large, destruction of the solid product may occur.
The organic acid halide is used in an amount of usually from 1 to 500 mol, preferably from 3 to 200 mol, and more preferably from 5 to 100 mol per mol of the titanium atom in the solid product, and usually from 0.01 to 1.0 mol, and preferably from 0.03 to 0.5 mol per mol of the magnesium atom in the solid product. When the amount is too large, destruction of the solid product may occur.
The compound having a Ti-halogen bond is used in an amount of usually from 10 to 10,000 mol, preferably from 30 to 5,000 mol, and more preferably from 100 to 3,000 mol per mol of the titanium atom in the solid product.
It is recommendable to use the compound having a Ti-halogen bond in combination with the electron donor compound (E1). In this case, the compound having a Ti-halogen bond is used in an amount of usually from 1 to 100 mol, preferably from 1.5 to 75 mol, and more preferably from 2 to 50 mol per mol of the electron donor compound.
When each compound mentioned above is subjected to several contacts, the above-mentioned amount is that per contact.
Usually, the solid catalyst component obtained according to the processes mentioned above are separated by solid-liquid separation, successively washed several times with an inert hydrocarbon solvent such as hexane and heptane, and then used for the polymerization. From a viewpoint of polymerization activity and stereospecificity polymerization ability of the catalyst, it is recommendable that the solid obtained by the solid-liquid separation is washed at a temperature of 50 to 120xc2x0 C. at least one time with a large amount of a halogenized hydrocarbon solvent such as monochlorobenzene or an aromatic hydrocarbon solvent such as toluene, successively washed several times with an aliphatic hydrocarbon solvent such as hexane, and then used for the polymerization.
Organoaluminum Compound
The xe2x80x9corganoaluminum compoundxe2x80x9d used in the present invention means a compound having at least one Al-carbon bond in the molecule. Typical examples thereof are those represented by the following formulas,
R19wAlY3xe2x88x92w and 
R20R21Alxe2x80x94Oxe2x80x94AlR22R23 
wherein R19 to R23 are independently of one another a hydrocarbon group having 1 to 20 carbon atoms, Y is a halogen atom, a hydrogen atom or an alkoxy group, and w is a number satisfying 2xe2x89xa6wxe2x89xa63.
Specific examples of said compound are trialkylaluminums such as triethylaluminum, tri-i-butylaluminum and trihexylaluminum; dialkylaluminum hydrides such as diethylaluminum hydride and di-i-butylaluminum hydride; dialkylaluminum halides such as diethylaluminum chloride; mixtures of trialkylaluminums and dialkylaluminum halides such as a mixture of triethylaluminum and diethylaluminum chloride; and alkylalumoxanes such as tetraethyldialumoxane and tetrabutyldialumoxane.
Among these, trialkylaluminums, mixtures of trialkylaluminums and dialkylaluminum halides and alkylalumoxanes are preferred. Triethylaluminum, tri-i-butylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, and tetraethyldialumoxane are particularly preferred.
Electron Donor Compound (E2)
As the electron donor compound (E2) used in the present invention, for example, oxygen-containing electron donor compounds such as ethers including diethers, ketones, aldehydes, carboxylic acids, organic acid esters, inorganic acid esters, organic acid amides, inorganic acid amides and acid anhydrides; and nitrogen-containing electron donor compounds such as ammonia, amines, nitriles and isocyanates are enumerated. Of these, inorganic acid esters and diethers are preferred, and alkoxysilicon compunds represented by the following formula are more preferred,
R3rSi(OR4)4xe2x88x92r 
wherein R3 is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, R4 is a hydrocarbon atoms having 1 to 20 carbon atoms, and r is a number satisfying 0xe2x89xa6r less than 4. All of R3 and all of R4 are the same or different from one another, respectively.
Particularly preferred electron donor compounds are alkoxysilicon compounds represented by the following formula,
R24R25Si(OR26)2 
wherein R24 is a C3xcx9c20 hydrocarbon group, whose carbon atom adjacent to Si is secondary or tertiary, R25 is a C1xcx9c20 hydrocarbon group and R26 is a C1xcx9c20 hydrocarbon group.
As R24, for example, branched chain alkyl groups such as isopropyl, sec-butyl, tert-butyl and tert-amyl groups; cycloalkyl groups such as cyclobutyl, cyclopentyl and cyclohexyl groups; cycloalkenyl groups such as a cyclopentenyl group; and aryl groups such as pheny and tolyl groups are enumerated. As R25, for example, straight chain alkyl groups such as methyl, ethyl, propyl, butyl and pentyl groups, branched chain alkyl groups such as isopropyl, sec-butyl, tert-butyl and tert-amyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; cycloalkenyl groups such as a cyclopentenyl group; and aryl groups such as pheny and tolyl groups are enumerated. As R26, hydrocarbon groups having 1 to 5 carbon atoms are preferred.
Specific examples of the alkoxysilicon compounds used as the electron donor compound (E2) are di-i-propyldimethoxysilane, di-i-butyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-ptropyldimethoxysilane, tert-butyl-n-butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysllane, tert-amyl-n-propyldimethoxysilane, tert-amyl-n-butyldimethoxysilane, i-butyl-i-propyl-dimethoxysilane, tert-butyl-i-propyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutyl-i-propyldimethoxysilane, cyclobutyl-i-butyldimethoxysilane, cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentyl-i-propyldimethoxysilane, cyclopentyl-i-butyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicylohexyldimethoxysilane, cyclohexylmethyldmethoxysilane, cyclohexylethyldimriethoxysilane, cyclohexyl-i-propyldimethoxysilane, cyclohexyl-i-butyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenymethyldimethoxysilane, phenyl-i-propyldimethoxysilane, phenyl-i-butyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, di-i-propyldiethoxysilane, di-i-butyldiethoxysilane, di-tert-butyldiethoxysilane, tert-butylmethyldiethoxysilane, tert-butylethyldiethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyldiethoxysilane, tert-amyl-n-propyldiethoxysilane, tert-amyl-n-butyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cycohexylmethyldiethoxysilane, cyclohexylethyldethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane and 2-norbornanemethyldiethoxysilane.
Polymerization of xcex1-olefin
The xe2x80x9cxcex1-olefinxe2x80x9d used in the present invention means that having not less than 3 carbon atoms. Examples of the xcex1-olefin are straight chain monolefin such as propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1 and decene-1; branched chain monolefin such as 3-methylbutene-1,3-methylpentene-1 and 4-methylpenetene-1; and vinylcyclohexane. The xcex1-olefin may be used each alone or in a mixture of two or more. Of these, it is preferred to use propylene or butene-1 each alone, or a mixed olefin containing propylene or butene-1 as a main component, and it is particularly preferred to use propylene alone or a mixed olefin containing propylene as a main component.
In the present invention, it is permitted to use an olefin mixture of at least two members selected from the group consisting of the xcex1-olefins mentioned above and ethylene. Further, it is permitted to additionally use a compound having several unsaturated bonds such as a conjugated diene and a non-conjugated diene as a comonomer. With respect to a polymerization method, it is also possible to carry out a hetero-block copolymerization, in which the polymerization is carried out not only at one stage but also at two or more stages.
The catalyst in accordance with the present invention can be obtained by contacting the aforementioned solid catalyst component, organoaluminum compound and electron donor compound (E2) with one another. How to contact them is not limited as far as the desired catalyst is obtained. With respect to a method for contacting them, for example, the following methods (1) and (2) are enumerated. In carrying out the contact, the aforementioned respective components may be used as they are, or may be diluted with a solvent.
(1) A mixture of the aforementioned three components is prepared to contact them.
(2) The aforementioned three components are separately supplied to a polymerization zone to contact them in the zone.
In the method (2), it is permitted to first prepare a contact product by contacting any two components among three, and then supply the contact product and the remaining one component to a polymerization zone. With respect to a method for supplying respective components to a polymerization zone, it is recommendable to carry out the supply in an inert gas such as nitrogen and argon under water free conditions.
In the present invention, the xcex1-olefin may be subjected to polymerization in the presence of the catalyst mentioned above, which polymerization is hereinafter referred to as xe2x80x9creal polymerizationxe2x80x9d, or subjected to pre-polymerization, followed by the real polymerization. Here, the xe2x80x9cpre-polymerizationxe2x80x9d means polymerization of a small amount of the olefin in the presence of the aforementioned solid catalyst component and organoaluminum compound.
It is recommendable to carry out the pre-polymerization in a slurry state. As a solvent used for forming the slurry state, for example, inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene and toluene are enumerated. It is allowed to use a liquid olefin in place of a part or whole of the solvent.
In the pre-polymerization, the organoaluminum compound is used in an amount of usually from 0.5 to 700 mol, preferably from 0.8 to 500 mol, and particularly preferably from 1 to 200 mol per mol of the titanium atom in the solid catalyst component.
An amount of the olefin to be pre-polymerized is usually from 0.01 to 1000 g, preferably from 0.05 to 500 g, and particularly preferably from 0.1 to 200 g per g of the solid catalyst component.
A concentration of the slurry in the pre-polymerization is preferably from 1 to 500 g-solid catalyst component/liter-solvent, and particularly preferably from 3 to 300 g-solid catalyst component/liter-solvent. A pre-polymerization temperature is preferably from xe2x88x9220 to 100xc2x0 C., and particularly preferably from 0 to 80xc2x0 C. A partial pressure of the olefin in the gas phase portion during the pre-polymerization is preferably from 0.01 to 20 kg/cm2, and particularly preferably from 0.1 to 10 kg/cm2, but the olefin which is liquid at that pressure and temperature for the pre-polymerization is not limited thereto. A time for the pre-polymerization is not particularly limited, and it is usually preferably from 2 minutes to 15 hours.
In the pre-polymerization, how to supply the solid catalyst component, the organoaluminum compound and the olefin is not limited. For example, the following methods (1) and (2) are enumerated. Here, it is permitted to use a chain transfer agent such as hydrogen in order to regulate a molecular weight of the polymer obtained.
(1) The solid catalyst component and the organoaluminum compound are contacted with each other, and thereafter the olefin is supplied.
(2) The solid catalyst component and the olefin are contacted with each other, and thereafter the organoaluminum compound is supplied.
Although how to supply the olefin is not limited, the following methods (1) and (2) are, for example, enumerated.
(1) The olefin is supplied one after another, while keeping an internal pressure of a polymerization zone to a predetermined level.
(2) The whole amount of the olefin predetermined is supplied at a time.
If desired, a part or the whole amount of the electron donor compound (E2) used for producing the catalyst as mentioned above may be present together in the pre-polymerization. The electron donor compound is used in an amount of usually from 0.01 to 400 mol, preferably from 0.02 to 200 mol, and particularly preferably from 0.03 to 100 mol per mol of the titanium atom in the solid catalyst component, and usually from 0.003 to 5 mol, preferably from 0.005 to 3 mol, and particularly preferably from 0.01 to 2 mol per mol of (ok?) the organoaluminum compound.
How to supply the electron donor compound in the pre-polymerization is not particularly limited. It is permitted to supply the electron donor compound independently from the organoaluminum compound, or contact both in advance and then supply the resulting product.
The olefin used in the pre-polymerization may be the same as or different from that used in the real polymerization.
In the real polymerization, the organoaluminum compound is used in an amount of usually from 1 to 1000 mol, and particularly preferably from 5 to 600 mol per mol of the titanium atom in the solid catalyst component.
In the real polymerization, the electron donor compound is used in an amount of usually from 0.1 to 2000 mol, preferably from 0.3 to 1000 mol. and particularly preferably from 0.5 to 800 mol per mol of the titanium atom in the solid catalyst component, and usually from 0.001 to 5 mol, preferably from 0.005 to 3 mol, and particularly preferably from 0.01 to 1 mole per mol of (ok?) the organoaluminum compound.
A temperature of the real polymerization is usually from xe2x88x9230 to 300xc2x0 C., and preferably from 20 to 180xc2x0 C. A polymerization pressure is not particularly limited, and from an industrial and economical point of view, it is usually from atmospheric pressure to 100 kg/cm2, and preferably from about 2 to 50 kg/cm2. The polymerization may be carried out in either a batch-wise manner or a continuous manner according to a slurry or solution polymerization method, wherein an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane and octane is used, or a bulk or gas phase polymerization method, wherein an olefin which is liquid at that polymerization temperature is used as a medium.
In the real polymerization, it is permitted to use a chain transfer agent such as hydrogen in order to regulate a molecular weight of the polymer obtained.